Surface-coating compositions containing n-(substituted indazolyl-n1-methyl)alkyleneimines

ABSTRACT

Compounds that have the structural formula   WHEREIN X represents halogen, nitro, amino, acetamino, aroylamino, or (halobenzylidiene)amino; Y represents hydrogen or halogen; R represents an alkylene group having from four to eight carbon atoms; and n represents an integer in the range of zero to 2 are used to protect surface-coating compositions from deterioration resulting from attach by fungi and bacteria. Illustrative of these compounds are N-(5-nitroindazolyl-N1methyl)hexamethyleneimine and N-(3-chloroindazolyl-N1methyl)piperidine.

Minieri 1 June 28, 1974 [54] SURFACE-COATING COMPOSITIONS 3,350,211 10/ 1967 Grecnwald 106/15 AF CONTAINING N (SUBSTITUTED 3,555,040 1/1971 Frick ct a1. 106/15 AF 3,637,736 1/1972 Minieri 106/15 AF INDAZOLYL'NI'METHYL) 3,646,210 2/1972 Johannes et a1... 106/15 AF ALKYLENEIMINES 3,766,207 10/1973 Minieri .1 106/15 AF Inventor: Pasquale P. Minieri, Woodside,

Assignee: Tenneco Chemicals, Inc., Saddle Brook, NJ.

[22] Filed: June 5, 1973 Appl. No.: 367,265

Related U.S. Application Data Continuation-impart of Ser. No. 201,159, Nov. 22, 1971, Pat. No. 3,766,192, which is a continuation-in-part of Ser. Nos. 689,812, Dec. 12, 1967, Pat. No. 3,641,050, and Ser. No. 141,999, May 10, 1971, Pat. No. 3,741,979.

References Cited UNITED STATES PATENTS 3,017,415 l/l962 Sarett et al. 106/15 AF Primary Examiner-Harry Wong, 'Jr. Attorney, Agent, or FirmEve1yn Berlow [57] ABSTRACT Compounds that have the structural formula hH,-N=R

ti/11515111 X represents halogen, nitro, amino,

10 Claims, No Drawings SURFACE-COATING coMPosmoNs CONTAINING N-(SUBSTITUTED HNDAZOLYL-Nl-METHYL) ALKYLENEIMINFS This is a continuation-in-part of my copending application Ser. No. 201,159, which was filed on Nov. 22, 1971 and which is now U.S. Pat. No. 3,766,192, and which is a continuation-in-part of copending applications Ser. No. 689,812, which was filed on Dec. 12, 1967 and which is now U.S. Pat. No. 3,641,050, and Ser. No. 141 ,999, which was filed on May 10, 1971 and which is now U.S. Pat. No. 3,741, 979.

This invention relates to surface-coating compositions that have improved resistance to deterioration resulting from attack by fungi, bacteria, and other microorganisms. More particularly, it relates to surfacecoating compositions that contain biocidal amounts of N-(substituted indazolyl-N'-methyl)alkyleneimines.

It is well known in the art that paints and varnishes often have inadequate resistance to the action of microorganisms. Some of these coating compositions, such as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyd resins, which are subject to attack by fungi and bacteria. Others, for example, aqueous dispersions of water-insoluble synthetic linear polymers, generally contain as plasticizers and thickeners materials that have their origin in animal or vegetable sources and that render the compositions suceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full scale utilization, particularly in those areas and in those applications that are conducive to such attack.

Various biocidal materials have been suggested for use in surface-coating compositions, but none has proven entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, while others have an adverse effect on the color, odor, or viscosity of the composition or undergo sulfide staining, and still others hydrolyze in alkaline aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching once the coating has been spread in a thin layer over the surface to be protected.

In accordance with this invention, it has been found that N-(substituted indazolyl-N- methyl)alkyleneimines are of particular value as bicoides in surface-coating compositions. These compounds, which are thoroughly compatible with the resinous binders that commonly are used in surfacecoating compositions and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by fungi and bacteria without adversely affecting the color, pH, viscosity, odor, and other physical properties of the surfacecoating compositions.

The biocidal compounds that are used in the surfacecoating compositions of this invention may be represented by the structural formula wherein X represents chlorine, bromine, fluorine, iodine, nitro, amino, acetamino, aroylamino, or (halobenzylidene)amino; Y represents hydrogen, chlorine, bromine, fluorine, or iodine; R represents an alkylene group having from four to eight carbon atoms; and n represents an integer in the range of zero to 2.

The most effective of these compounds as biocides in surface-coating compositions are those represented by the structural formula fia wherein X represents nitro, chlorine, or (chlorobenzylidene)amino; Y represents hydrogen or chlorine; R represents a branched or unbranched alkylene group having five or six carbon atoms; n represents an integer in the range of zero to 2; and then n represents zero, Y represents chlorine. Illustrative of these preferred biocidal compounds are the following: N-(3- chloroindazolyl-N -methyl)piperidine, N-(3-chloro-5- nitroindazolyl-N -methyl )piperidine, N-( 5 ,6- dinitroindazolyl-N-methyl)piperidine, N 6- nitroindazolyl-N -methyl )piperidine, N-( 5 chloroindazolyl-N -methyl )-3-methylpiperidine, N-( 3- chloroindazolyl-Nmethyl)hexamethyleneimine, N-( 5- chloroindazolyl-N -methyl)hexamethyleneimine, N-(6- chloroindazolyl-N -methyl)hexamethyleneimine, N- 3 ,5-dichloroindazolyl-N -methyl hexamethyleneimine, N-( 3 ,6-dichloroindazolyl-N methyl)hexamethyl-eneimine, N-(3,5,6- trichloroindazolyl-N-methyl)hexamethyleneimine, N- (3-chloro-5-nitroindazolyl-N -methyl )hexamethyleneimine, N-(3-chloro-6-nitroindazolyl-N'-methyl)hexamethyleneimine, N-(3,5-dichloroindazolyI-N- methyl)hexamethyleneimine, N-(5,6-dinitroindazolyl- N-methyl)hexamethyleneimine, and the like.

The novel compounds may be prepared by any suitable and convenient procedure. For example, they may be prepared by heating the appropriate N- hydroxymethyl-substituted-indazole with an alkyleneimine. The reaction is preferably carried out in a solvent, such as benzene, toluene, pyridine, or acetone, at the reflux temperature of the reaction mixture. The N- hydroxymethylsubstituted-indazoles may be prepared by the procedure described in U.S. Pat. No. 3,637,736.

In a preferred embodiment of this invention, the N- (substituted indazolyl-N -methyl)alkyleneimines are used to impart fungal and bacterial resistance to dried films of protective or decorative coating compositions that have been applied to a surface. When they are added in the amount of about 0.1 percent to 5 percent, and preferably 0.25 percent to 2 percent, based on the weight of the surface-coating composition, these compounds provide excellent and prolonged resistance to deterioration resulting from attack by fungi, bacteria, and other microorganisms without adversely affecting the physical properties of the surface-coating compositions or of the dried films of these compositions.

The N-(substituted indazolyl-N'- methyl)alkyleneimines can be used to impart fungal and bacterial resistance to a wide variety of surface- 3 coating compositions including both organic solventbased and water-based caoting systems. The surfacecoating compositions generally contain about percent to 60percent by weight of an organic, waterinsoluble, film-forming, resinous binder that is a synthetic linear addition polymer and/or an oleoresinous binder.

Illustrative of the synthetic linear addition polymers that can be used as the binder in the compositions of this invention are the following: polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with vinyl chloride or acrylonitrile; copolymers of vinyl chloride with acrylonitrile or vinylidene chloride; polyethylene; polyisobutylene; copolymers of styrene with butadiene, acrylonitrile, or maleic anhydride; copolymers of acrylic acid" esters ormethacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrenercopolymers of the aforementioned acrylic acid esters, the aforementioned methacrylic acid esters, and acrylic acid; and mixtures thereof. Suitable oleo-resinous binders include drying oils, bodied drying oils, oleo-resinous varnishes, alkyd resins, and mixtures thereof. v

in addition to the resinous binder andthe biocidal compound, the surface-coating compositions may contain various auxiliary materials, such as pigments, extenders, so|vents,-dyes, defoaming agents, driers, emulsifiers, plasticizers, and thelike in the amounts ordinarily used for these purposes. A

The biocidal compounds may be incorporated into the surface-coating compositions by any convenient procedure. For example, they can be combined with the pigments and other ingredients to form a pigment phase that is mixed with the resinous binder and water or organic solvent to form the surface-coating composition. Alternatively, they can be added to a composition that contains the resinous bindenpigment, and water or organic solvent. The biocidal compounds can be added as such to the other ingredients, or they can be added as a solution in, for example, an alcohol, ether, hydrocarbon, or ketone. v

The invention is further illustrated by the following examples: r

EXAMPLE 1 To 200ml. of toluene, which had been dried by azeotropic distillation, was added with stirring 18.3 grams (0.1 mole) of N'-hydroxymethyl-3-chloroindazole and 10 grams (0.1 mole) of hexamethyleneimine. The reaction mixture was heated at its reflux temperature until 1.8 ml. of water had been evolved and then for an additional 30 minutes at this temperature. The reaction mixture was then heated ona water bath under reduced pressure until it reached constant weight. There was obtained 27.7 grams of N-(3-chloroindazolyl-N'- "methyl)hexamethyleneimine, which contained. 63.35

( 1.8 ml.)'of water had been evolved and then for an additional 30 minutes at this temperature. The reaction mixture was heated on a water bath under reduced pressure until itreached constantweight. There was obtained a 100 percent yield of N-(5-chloroindazolyl- N -methyl)hexamethyleneimine, a liquid which solidified on standing. Theproduct contained 64.1 percent C, 6.75 percent H, 16.5 percent N, and 13.5 percent C1 (calculated, 65.2 percent C, 6.52 percent H, 15.2 percent N, and 12.8 percent Cl). l

EXAMPLE 3 EXAMPLES 4 9 A series of N-(substitut'ed indazolyl-N-methyl)hexamethyleneimines was prepared by the procedures described in Examples 2 and 3. .The compounds prepared andtheir properties are given in Table 1.

TABLE I,

' Melting Ex. Compound Method of Yield Point No. Preparation (C.)

4 N-[6-(3,4-dichlorobenzylidene) vEx. 2 100.0 Oil aminoindazolyl-N -methyl] hexamethyleneimine 5 N-(3-chloro-5rnitroindazolyl- Ex. 2- 98.7 Semi- N -methyl)hexamethyl- 1 solid eneimine 6 N-(3-chloro-6-nitroindazolyl- Ex. 3 95.3 74-81 N -methyl)hexamethylene- I v imine 7 N-(S-nitroindazolyl-N-methyl)- Ex. 3 93.5 .72-82 hexamethyleneimine 8 N-(G-nitroindazolyl-N-methy1)- Ex. 3 91.7 73-83 hexamethyleneimine 9 N-(5,6-dinitroindazolyl-N Ex. 3 96.6 87-96 methyl)hexamethyleneimine EXAMPLE 10 A mixture of 200 ml. of benzene, 18.3 grams (0.1 mole) of N -hydroxymethyl-5,6-dinitroindazole, and 9.2 grams (0.1 lmole) of piperidine was heated at its reflux temperature until the theoretical quantity (1.8 ml.) of water had been evolved and then for an additional minutes at this temperature-The reaction mixture was heated on a'water bath under reduced pressure until it reached constant weight. There was obtained 29 grams (95.3 percent yield) of N-(5,6-dinitroindazolyl- N-methyl)piperidine, which melted at 130l33C. and contained 50.48 percent C, 4.90 percent H, and 22.7 percent N (calculated, 51.1percent C, 4.92 percent H, and22.95'pe rcent N). The structure of the compound was confirmed by infra-red analysis.

EXAMPLE 1 1 mole) of piperidine was heated on a boiling water bath for 30 minutes and then cooled to room temperature. When m1. of water had been added to the reaction I mixture, it separated into aqueous and oil phases. The

3,821 ,1 8O 6 oil phase was separated, and it solidified on standing. Pam by weigh It was filtered, washed with water, and vacuum dried at Wmr I68 60C. The resulting crude product was recrystallized Alkyl aryl t g y f 6 riton from l1gro1n. There was obtained 24 grams (93.8 per- 25% Aqueous Solution of sodium cent yield) of N-( 6-nitro1ndazolyl-N- 5 salt of maleic anhydride/diiso- 27 methyl)piperidine, which melted at 9496C. and conbuylene Defoamer 1.. tamed 59.98 percent C, 6.19 percent H, and 22.05 per- 2% Aqueous solution of hydroxycent N (calculated, 59.9 percent C, 6.15 percent H, ethylcellumse 300 d 22 l 5 N Ethylene glycol 60 an percent The structure of the compound Tiganium dioxide 750 was confirmed by infra-red analysis. g 90 Calcium carbonate 375 EXAMPLES 12 8 Ammonium hydroxide (28% aqueous 6 1 solution) 46? 1 Aqueous dispersion containing c A series of N (substitued indazolyl N acrylic ester polymer (66% ethyl methyl)pipendmes was prepared by the procedures deacrylate, 32.5% methyl acrylate, 1642 scribed in Examples 10 and l 1. In each case the strucl5 and ac'dl ture of the compound was confirmed by infra-red analysis. The compounds prepared and their properties are given in Table 11. This paint had the following properties:

Table 11 Melting Analysis (calculated) Ex. Method of Yield Point N0. Compound Preparation (C.) C H N Cl 12 N-(3-chloroindazolyl-N-methyl) Ex. 10 100.0

piperidine l3 N-(3-ch1oro-5-nitroindazolyl-N'- Ex. 11 96.7 106-114 54.99 5.25 20.09 methyl)piperidine (52.8 (5.08) (18.95) 14 N-(S-nitroindazolyl-N-methyl) Ex. 11 91.0 89-- 91 60.6 6.18 22.4 piperidine (60.0 (6.15) (21.6 15 N-(5chloroindazolyl-N-methyl) Ex. 11 97.8 104-105 16.1 13.6

piperidine (16.8 (14.2 16 N-(3.5-dichloroindazolyl-N'- Ex 11 96.0 75- 78 53.96 4.58 14.7 25.7

methyl)piperidine (54.8 5.28 (14.8 (25.0 17 N-(S-chloroindazolyl-N'-methyl)- Ex 11 92.2 59- 65 62.9 6.50 15.53 14.39

3-methylpiperidine (63.7 (6.83) (15.9 (13.45) 18 N-(5.6-dinitroindazolyl-N'- Ex 10 99.0 108-115 53.27 5.27 21.3 methyl)-3-methylpiperidine (51.1 (5.17) (21.3

EXAMPLE 19 Viscosity 72 K.U. Brookfield Viscosity A. A polyvinyl acetate latex paint was prepared by 40 3 p p 2582cps. mixing together the following materials: fienowness Index Parts by Weight This paint has the following properties as determined by standard paint testing procedures:

Viscosity K.U. Brookfield Viscosity 800 cps.

(No. 4 spindle, 60 rpm) pH 7.8 Yellowness Index 3.0 65

B. An acrylic latex paint was prepared by mixing together the following materials:

C. An exterior house paint was prepared by mixing together the following materials:

Parts by Weight Basic lead carbonate 288 Zinc oxide 232 Titanium dioxide (rutile) 149 Talc 260 Linseed oil 242 Bodied linseed oil 1 14 Mineral spirits 1 14 Antiskinning agent 2 Manganese naphthenate (6%) 2.27 Lead naphthenate (24%) l 1.3

EXAMPLE 20 The paints whose preparation was described in Example 19 were evaluated by means of an agar diffusion assay. In this test, agar is inoculated with the test organism, the paint to which 2 percent by weight of a biocide has been added is placed in a well out from the agar,

and after incubation at 28C. and 85-95 percent relative humidity, the activity of the biocide is measured by zones of inhibition. The biocidal compounds tested and the results obtained are given in Table Ill. In this table 20 Zone of inhibition in mm.

No zone of inhibition; no growth Tr Trace zone of inhibition Not tested Bacteria A Bacillus subtilis Aerobacter aerogenes 1 that contains 0.10 percent to 5 percent, based on the weight of the composition, of the biocidal compound.

3. A surface-coating composition as setforth in claim 1 wherein the organic, water-insoluble, film-forming,

4. A surface-coating composition as set forth in claim 1 wherein the organic, water-insoluble, film-forming, i usb n sr p y nyl se ate g a F gP f P 5. A surface-coating composition as set forth in claim ixe inocu um consistln o .aeru 1 53 ATCC 10145 aemgenges ATCC g: and 1 wherein the biocidal compound has the structural three unidentified strains of Bacillus formula Fungi E Pullularia pullulans F Penicillium crustosum G Aspergillus niger 1 --CY' Each of the other N-(substituted mdazolyl-N ILL I l o I n n methyl)-alkyleneimmes herein disclosed can be used m a similar manner to inhibit or prevent the growth of mi- N croorganisms in surface-coating compositions. 1HN=R Table 111 Effect on Biocidal Activity Paint Bacteria Fuggi Biocide Paint pH Color A B D E F G Product of Ex. 1 PVA 8.4 Off-white 20-6 20-5 20-2 Tr 20-6 20-2 Acrylic 9 3 Off-white 20-3 20-1 20-2 20-2 20-3 20-1 0il Off-white 20-4 20-5 20-2 Product of Ex. 6 PVA 8.2 Yellow 20-6 20-2 20-1 20-5 Acrylic 9 7 Yellow 20-3 Tr 20-4 Tr Tr Tr Oil Yellow 20-1 20-1 Tr Product of Ex. 7 PVA 8.3 Off-white 20-5 20-1 Tr 20-5 Acrylic 9.6 Beige 20-5 20-1 Tr 20-3 Tr Tr Tr Oil Beige 20-5 20-3 Tr Product of Ex. 8 PVA 8.4 Yellow 20-6 20-3 20-1 20-3 Acrylic 97 Beige 20-3 Tr 20-5 Tr Tr Tr on Beige 20-1 20-2 Tr Product of Ex. 9 PVA 83 Yellow 20-2 20-1 20-2 20-7 Acrylic 9.7 Yellow 20-5 20-1 20-3 Tr Tr Tr Oil Yellow Tr Tr Tr Product of Ex. 12 PVA 8.5 White 20-3 20-3 20-1 20-4 Tr 20-2 Tr Acrylic 9.7 White Tr 20-4 20-4 20-1 20-1 20-6 20-1 Oil White Tr Tr Tr Bis( phenylmercury )dodecenyl- PVA 6.9 Off-white 20-10 20-2 20-7 20-17 20-6 20-13 succinate (Super Ad-ir) Acrylic 8.4 Off-white 20-9 20-6 20-9 20-1 20-10 Oil Off-White 20-8 20-10 20- 10 2.3.5.6-Tctrachloro-4- (methyl- 7.3 Off-White 4 20-8 0 0 20-13 20-10 20-6 sullonyhpyridinc (Dow 1013) AcryTic 9.2 Off-white 7K8 (l 20 20-7 -6 Oil Beige 20-12 20-10 20-) What is claimed is:

l. A surface-coating composition that comprises (a) an organic, water-insoluble, film-forming, resinous binder and (b) a biocidally effective amount of a biocidal compound having the structural formula wherein X represents nitro, chlorine, or (chlorobenzy1idene)amino; Y represents hydrogen or chlorine; R represents an alkylene group having from five to six carbon atoms; n represents aninteger in the range of zero to 2; and when n represents zero, Y represents hlorine; s.

6. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-(3- h ere nda .rNlflsth lpirsrid e- 7. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-( 3-ch1oro-6- .ni t naze rw-m amst x nei 8. A surface-coating composition as set forth in claim I wherein the biocidal compound is N-( 3,5- dichloroindazo1yl-N-methyl)hexamethyleneimine.

3,821,180 7 o n..n.rif.wtfl 9.Asurface-coating compositionasset tofth in claim 10. A Surface-coating conioosition as set forth in 1 wherein the biocidal compound is N-(3- claim 1 wherein the biocidal compound is N-(5,6- ehl oroinoazolyi-Nf r nethyi)hexqmethyienei nine dinitroindazolyl-N-methyl)hexamethyleneimine. 

2. A surface-coating composition as set forth in claim 1 that contains 0.10 percent to 5 percent, Based on the weight of the composition, of the biocidal compound.
 3. A surface-coating composition as set forth in claim 1 wherein the organic, water-insoluble, film-forming, resinous binder is selected from the group consisting of oleoresinous binders, synthetic linear addition polymers, and mixtures thereof.
 4. A surface-coating composition as set forth in claim 1 wherein the organic, water-insoluble, film-forming, resinous binder is polyvinyl acetate.
 5. A surface-coating composition as set forth in claim 1 wherein the biocidal compound has the structural formula
 6. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-(3-chloroindazolyl-N1-methyl)piperidine.
 7. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-(3-chloro-6-nitroindazolyl-N1-methyl)hexamethyleneimine.
 8. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-(3,5-dichloroindazolyl-N1-methyl)hexamethyleneimine.
 9. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-(3-chloroindazolyl-N1-methyl)hexamethyleneimine.
 10. A surface-coating composition as set forth in claim 1 wherein the biocidal compound is N-(5,6-dinitroindazolyl-N1-methyl)hexamethyleneimine. 